Polyoxometalate materials, metal-containing materials, and methods of use thereof

ABSTRACT

Polyoxometalate topical compositions for removing contaminants from an environment and methods of use thereof are disclosed. An embodiment of the polyoxometalate topical composition includes a topical carrier and at least one polyoxometalate, with the proviso that the polyoxometalate is not H 5 PV 2 Mo 10 O 40 ; K 5 Si(H 2 O)Mn III W 11 O 39 ; K 4 Si(H 2 O)Mn IV W 11 O 39 ; or K 5 Co III W 12 O 40 . Another embodiment relates to a method for removing a contaminant from an environment, including contacting the polyoxometalate topical composition with the environment containing the contaminant for a sufficient time to remove the contaminant from the environment. An additional embodiment relates to a modified material for removing a contaminant from an environment, wherein the modified material includes (1) a material comprising a topical carrier, a powder, a coating, or a fabric, and (2) a metal compound including a transition metal compound, an actinide compound, a lanthanide compound, or a combination thereof, wherein the metal compound is not a polyoxometalate.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a Divisional of 09/689,231, filed on Oct. 11, 2000, now U.S. Pat. No. 6,723,349, which claims priority upon U.S. provisional application Ser. No. 60/158,952, filed on Oct. 12, 1999, the contents of which Provisional Application are herein incorporated by this reference in their entirety.

FIELD OF THE INVENTION

The present invention relates to materials containing a polyoxometalate or a metal compound, wherein the metal compound is not a polyoxometalate The invention further relates to methods for removing a contaminant from an environment by contacting the environment with a polyoxometalate material or a non-polyoxometalate material.

BACKGROUND OF THE INVENTION

Decreasing the potential danger of contaminants from the environment has long been a significant issue. For example, the removal of offensive odors originating from cigarette smoke, sweat, exhaust gases, and rotten food in the work place, the home, and elsewhere would be quite beneficial to the public-at-large. Additionally, materials that can remove highly toxic contaminants, such as chemical warfare agents (CWAs), from the environment can ultimately reduce a soldier's exposure to the agent. Examples of materials that would be useful include creams, powders, coatings, and fabrics

Creams, also referred to as topical skin protectants (TSPs), have been developed to protect soldiers from the threat of dermal exposure to chemical warfare agents TSPs require an inert material which can be applied on the skin in a thin layer to form an antipenetrant barrier to CWAs or other contact irritants that will not interfere excessively with normal skin functions. A preferred TSP affords protection against CWAs and other toxic or irritating materials in all of the forms in which they might be encountered (e.g., liquid, aerosolized liquid and vapor). Perhaps the best-known vesicant CWA is 2,2′-dichlorodiethylsulfide (also known as “HD” or “sulfur mustard”), which was first used during World War I. Improved TSPs, however, are needed for protecting military personnel and civilians from percutaneous exposure to CWAs and protecting the skin from contact dermatitis arising from other sources as well

U.S. Pat. No 5,607,979 to McCreery discloses topical creams formed from about 35% to about 50% fine particulates of certain poly(tetrafluoroethylene) (PTFE) resins dispersed in perfluorinated polyether oils having viscosities from about 20 cSt to about 350 cSt. The creams afford protection against chemical warfare agents such as sulfur mustard (HW), lewisite (L), sulfur mustard/Lewisite mixtures (HL), pinacolyl methylphosphonofluoridate (soman or GD), thickened soman (TGD), and O-ethyl-S-2-diisopropylaminoethyl methylphosphonothiolate (VX). These creams, however, can only provide limited exposure to a CWA for a short period of time. Furthermore, the creams cannot convert the CWA to an inactive form, which will reduce the overall toxicity of the CWA.

Thus, there is a need for a material, which is also referred to herein as a support, that can remove a contaminant from the environment for an extended period of time The incorporation of a polyoxometalate (herein referred to as “POM”) into a material such as a cream, coating, powder, or fabric, is one approach to removing a contaminant from an environment. Gall et al. (Chem. Mat. 8, pp. 2523–2527, 1996) disclose the immobilization of H₅PV₂Mo₁₀O₄₀ on carbon cloth in order to determine the ability of H₅PV₂Mo₁₀O₄₀ to remove sulfur containing compounds from toluene. Johnson et al. (Proc. ERDEC Sci. Conf. Chem. Biol. Def. Res., 1998, pp. 393–399) disclose suspending H₅PV₂Mo₁₀O₄₀; K₅Si(H₂O)Mn^(III)W₁₁O₃₉, K₄Si(H₂O)Mn^(IV)W₁₁O₃₉; or K₅Co^(III)W₁₂O₄₀ in a perflouropolyether barrier cream to determine the creams ability to detect the presence of mustard gas. Johnson et al., however, is not concerned with the removal of the mustard gas from the gas phase.

The prior art also discloses the incorporation of polyoxometalates into powders and coatings. For example, U.S. Pat. No. 5,356,469 to Curcio et al. disclose a metal pigment composition suitable for the formation of a coating composition The coating composition is composed of a solvent, a metal pigment, at least one phosphosilicate pigment, and at least one heteropoly anion. The metal pigment particles possess increased stability against attack by water. Japanese patent application number 4054127 to Terumo Corp. discloses the use of heteropoly acid salts as anti-tumor agents. The heteropoly acid salts can be administered in the form of a powder or suspended in solution. Although the prior art discloses a number of different applications of polyoxometalate powders or coatings, the art does not disclose the use of a powder or coating containing a polyoxometalate to remove a contaminant from the environment.

In light of the above, it would be very desirable to have an article and a method of using an article for the removal of toxic and/or malodorous compounds without adding stoichiometric amounts of additives or compounds to the article. The present invention solves such a need in the art while providing surprising advantages. The present invention herein incorporates a polyoxometalate (POM) into a material such as a topical carrier, powder, or coating, which greatly increases the ability of the to remove a contaminant from the environment. The present invention also incorporates a metal compound, wherein the metal compound is not a polyoxometalate, into a in order to remove a contaminant from the environment.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the consumption of oxygen and formation of CEESO as a function of time.

FIG. 2 shows CEESO formation as a function of time using 1 Au/2Cu/3 NO₃, 2Cu/3NO₃; and 1 Au/3NO₃.

SUMMARY OF THE INVENTION

In accordance with the purpose(s) of this invention, as embodied and broadly described herein, this invention, in one aspect, relates to a polyoxometalate topical composition for removing a contaminant from an environment, comprising a topical carrier and at least one polyoxometalate, with the proviso that the polyoxometalate is not H₅PV₂Mo₁₀O₄₀; K₅Si(H₂O)Mn^(III)W₁₁O₃₉, K₄Si(H₂O)Mn^(IV)W₁₁O₃₉; or K₅Co^(III)W₁₂O⁴⁰

The invention further relates to a method for removing a contaminant from an environment, comprising contacting the polyoxometalate topical composition of the present invention with the environment containing the contaminant for a sufficient time to remove the contaminant from the environment.

The invention further relates to a method for removing a contaminant from an environment, comprising contacting a polyoxometalate powder or a polyoxometalate coating with the environment containing the contaminant for a sufficient time to remove the contaminant from the environment.

The invention further relates to a modified polyoxometalate, wherein the modified polyoxometalate comprises the admixture of (1) a polyoxometalate and (2) a cerium compound, a silver compound, a gold compound, a platinum compound, or a combination thereof.

The invention further relates to a method for removing a contaminant from an environment, comprising contacting a modified material with the environment containing the contaminant for a sufficient time to remove the contaminant from the environment, wherein the modified material comprises (1) a material and (2) a metal compound comprising a transition metal compound, an actinide compound, a lanthanide compound, or a combination thereof, wherein the metal compound is not a polyoxometalate.

The invention further relates to a modified material for removing a contaminant from an environment, wherein the modified material comprises (1) a material comprising a topical carrier, a powder, a coating, or a fabric, and (2) a metal compound comprising a transition metal compound, an actmide compound, a lanthanide compound, or a combination thereof, wherein the metal compound is not a polyoxometalate.

The invention further relates to an article comprising the modified of the present invention.

Additional advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The advantages of the invention will be realized and attained by means of the elements and combinations. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention.

DETAILED DESCRIPTION OF THE INVENTION

The present invention may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the Examples included therein.

Before the present methods and articles are disclosed and described, it is to be understood that this invention is not limited to specific synthetic methods or to particular formulations, as such may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting.

In this specification and in the claims which follow, reference will be made to a number of terms which shall be defined to have the following meanings.

The singular forms “a,” “an” and “the” include plural referents unless the context clearly dictates otherwise

“Optional” or “optionally” means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.

In accordance with the purpose(s) of this invention, as embodied and broadly described herein, this invention, in one aspect, relates to a polyoxometalate topical composition for removing a contaminant from an environment, comprising a topical carrier and at least one polyoxometalate, with the proviso that the polyoxometalate is not H₅PV₂Mo₁₀O₄₀; K₅Si(H₂O)Mn^(III)W₁₁O₃₉; K₄Si(H₂O)Mn^(IV)W₁₁O₃₉; or K₅Co^(III)W₁₂O₄₀

The invention further relates to a modified polyoxometalate, wherein the modified polyoxometalate comprises the admixture of (1) a polyoxometalate and (2) a cerium compound, a silver compound, a gold compound, a platinum compound, or a combination thereof.

The invention further relates to a modified material for removing a contaminant from an environment, wherein the modified material comprises (1) a material comprising a topical carrier, a powder, a coating, or a fabric, and (2) a metal compound comprising a transition metal compound, an actinide compound, a lanthanide compound, or a combination thereof, wherein the metal compound is not a polyoxometalate.

The invention further relates to an article comprising the modified material of the present invention.

Many polyoxometalates known in the art can be used in the present invention to remove a contaminant from an environment. Polyoxometalates are also referred to in the art as heteropoly compounds, heteropoly acids, isopoly compounds, and isopoly acids, which are subsets of polyoxometalates. Examples of polyoxometalates useful in the present invention are disclosed in Pope, M. T in Heteropoly and Isopoly Oxometalates, Springer Verlag, 1983, and Chemical Reviews, vol. 98, no. 1, pp 1–389, 1998, which are incorporated by this reference in their entirety.

The selection of the polyoxometalate used in the present invention is dependent upon the contaminant or contaminants to be removed from the environment. In one embodiment, the polyoxometalate has the formula 1 of [V_(k)Mo_(m)W_(n)Nb_(o)Ta_(p)M_(q)X_(r)O_(s)] [A], wherein M is at least one f-block element or d-block element having at least one d-electron, wherein M is not vanadium, molybdenum, tungsten, niobium, or tantalum, X is at least one p-, d-, or f-block element, wherein X is not oxygen; k is from 0 to 30, m is from 0 to 160; it is from 0 to 160; o is from 0 to 10; p is from 0 to 10; q is from 0 to 30; r is from 0 to 30; s is sufficiently large that y is greater than zero; and y is greater than zero, wherein the sum of k, m, n, o, and p is greater than or equal to four; and the sum of k, m, and q is greater than zero, and A is one or more different counterions In one embodiment, s is from 19 to 460. The charge on the POM, y, is dictated by the values of k, m, n, o, p, q, r and s. The p-, d-, and f-block elements can exist in any oxidation state.

Generally, M can be any d-block element having at least one d-electron or f-block element having at least one f-electron. Typically, M comprises titanium chromium, manganese, cobalt, iron, nickel, copper, rhodium, silver, palladium platinum, mercury, ruthenium, cerium, or europium. In a preferred embodiment, M comprises manganese, cobalt, or ruthenium. In another embodiment, X comprises phosphorus, silicon, aluminum, boron, cobalt, zinc, or iron. When the polyoxometalate has the Keggin structure XM₁₂, then it is possible for X and at least one M to be the same d- or f-block element. Not wishing to be bound by theory, it is believed that the metal ion M of the polyoxometalate of the present invention is responsible for removing the contaminant from the gas phase, while X, when present, provides structural integrity to the polyoxometalate.

In one embodiment, the sum of k and q is greater than or equal to one, the sum of k, m, n, o, p, and q is 12, and s is 40. In yet another embodiment, k is not zero In another embodiment, q is not zero

In a more specific embodiment, when the polyoxometalate has the formula 1, the polyoxometalate has the formula [X^(g+)V_(b) ^(f+)M_(c) ^(h+)Z_(12-b-c) ²⁺O_(x)[^(u−)[A], wherein X is at least one p-, d-, or f-block element; g is greater than or equal to 2; M is at least one f-block element or d-block element having at least one d-electron, wherein M is not vanadium, h is from 1 to 7; i is from 5 to 6; j is from 4 to 5; x is 39 or 40 Z is tungsten, molybdenum, niobium, or a combination thereof; b is from 0 to 6; c is from 0 to 6, u is from 3 to 9; and A is a counterion. The values of u, x, i, b, c, g, h, and j will vary depending upon the selection of X, M, and Z. The variables are related to one another and can be derived by the following formula: u=2(x) −i(12-b-c)-g-c(h)-b(j) The values of h, i and j are average charges, and depend upon the selection and number of X, M, Z, and V present in the POM. For example, when Z is Nb⁺⁵ and Nb⁺⁶ (i.e., two Nb atoms present in the POM), the value of i+ is 5.5.

In a more specific embodiment, when the polyoxometalate has the formula 1, the polyoxometalate has the formula [X^(g+)V_(b) ^(f+)Z_(12−b) ¹⁺O₄₀]^(u−)[A], wherein X is at least one phosphorus, silicon, aluminum, boron, zinc, cobalt, or iron; b is from 1 to 6, and u is from 3 to 9.

In a more specific embodiment, when the polyoxometalate has the formula 1, the polyoxometalate has the structure [X^(g+M) _(c) ^(h+)Z_(12−c) ¹⁺O₄₀]^(a−)[A], wherem X is at least one phosphorus, silicon, aluminum, boron, zinc, cobalt, or iron; c is from 1 to 6, and u is from 3 to 9.

In a more specific embodiment, when the polyoxometalate has the formula 1, the polyoxometalate has the formula [X₂ ^(r+)V_(u) ^(s+)M_(v) ^(t+)Z_(18-u-v) ^(y+)O_(z)]^(w) [A], wherein X is at least one p-, d-, or f-block element; r is greater than or equal to 1, M is at least one f-block element or d-block element having at least one d-electron, wherein M is not vanadium, t is from 1 to 7; s is from 4 to 5; Z is tungsten, molybdenum, niobium, or a combination thereof; u is from 0 to 9; v is from 0 to 9; y is from 5 to 6; z is 61 or 62; w is greater than or equal to 4; and A is a counterion. Similar to the formula above, the values of r, s, t, u, v, w, y, and z, will vary depending upon the selection of X, M, and Z. The variables are related to one another and can be derived by the following formula w=2(z) −y(18-u-v) −2r−v(t) −u(s) The values of r, s, t, and y are also average charges, and depend upon the selection and number of X, M, Z, and V atoms present in the POM.

In a more specific embodiment, when the polyoxometalate has the formula 1, the polyoxometalate has the formula [X₂ ^(r+)V_(u) ^(s+)Z_(18−g) ^(y+)O₆₂]^(w−)[A], wherein X is at least one phosphorus, sulfur, silicon, aluminum, boron, zinc, cobalt, or iron; u is from 1 to 9, and w is greater than or equal to 4.

In a more specific embodiment when the polyoxometalate has the formula 1, the polyoxometalate has the formula [X₂ ^(r+)M_(v) ^(t+)Z_(18−v) ^(y+)O₆₂]^(w−)[A], wherein X is at least one phosphorus, sulfur, silicon, aluminum, boron, zinc, cobalt, or iron; v is from 1 to 9; and w is greater than or equal to 4

In a more specific embodiment, when the polyoxometalate has the formula 1, the polyoxometalate has the formula [YV_(p)Z_(12−p)O₄₀][A], wherein Y is phosphorus, silicon, or aluminum; Z is tungsten or molybdenum; p is from 1 to 6, and A is a counterion. In one embodiment, Y is phosphorus and Z is molybdenum. In one embodiment, Y is phosphorus and Z is tungsten. In one embodiment, Y is silicon and Z is molybdenum. In one embodiment, Y is silicon and Z is tungsten. In one embodiment, Y is aluminum and Z is tungsten. In one embodiment, Y is aluminum and Z is molybdenum.

In a more specific embodiment, when the polyoxometalate has the formula 1, the polyoxometalate has the formula [X^(g+)V_(b)M^(h+) _(c)Z_(12-b-c)O₄₀]^(u−)[A], wherein X is at least one p-, d-, or f-block element; g+ is the charge of X; M is at least one f-block element or d-block element having at least one d-element, wherein M is not vanadium, h+ is the charge of M; Z is tungsten, molybdenum, niobium, or a combination thereof; b is from 0 to 6; c is from 0 to 6, wherein the sum of b and c is greater than or equal to one; u is greater than 3; and A is a counterion.

In a more specific enbodiment, when the polyoxometalate has the formula 1, the polyoxometalate has the formula [X^(g+)M^(h+) _(c)Z_(12−c)O₄₀]^(u−)[A], wherein X is at least one phosphorus, silicon, aluminum, boron, zinc, cobalt, or iron; Z comprises tungsten, molybdenum niobium, or a combination thereof; b is from 1 to 6; and u is greater than 3.

In a more specific embodiment, when the polyoxometalate has the formula I, the polyoxometalate has the formula [X^(g+)M^(h+) _(c)Z_(12−c)O₄₀]^(u−)[A], wherein X is at least one phosphorus, silicon, aluminum, boron, zinc, cobalt, or iron; Z comprises tungsten, molybdenum, niobium, or a combination thereof; M is at least one f-block element or d-block element having at least one d-electron; c is from 1 to 6; and u is greater than 3

In a more specific embodiment, when the polyoxometalate has the formula 1, the polyoxometalate has the formula [X¹⁺ ₂ V₃M³⁺ _(v)Z_(18-u-v)O₆₂]^(w−)[A], wherein X is at least one p-, d-, or f-block element; i+ is the charge of X; M is at least one d- or f-block element, wherein M is not vanadium; j+ is the charge of M, Z is tungsten, molybdenum, niobium, or a combination thereof, u is from 0 to 9; v is from 0 to 9, wherein the sum of u and v is greater than or equal to one; w is greater than or equal to 4, and A is a counterion.

In a more specific embodiment, when the polyoxometalate has the formula 1, the polyoxometalate has the formula [X¹⁺ ₂ V_(u)Z_(18−u)O₆₂]^(w−)[A], wherein X is at least one phosphorus,sulfur, silicon, aluminum, boron, zinc, cobalt, or iron; Z comprises tungsten, molybdenum, niobium, or a combination thereof; u is from 1 to 9, and w is greater than or equal to 4.

In a more specific embodiment, when the polyoxometalate has the formula 1, the polyoxometalate has the formula [X¹⁺ ₂M³⁺ _(v)Z_(18−v)O₆₂]^(w−)[A], wherein X is at least one phosphorus, sulfur, silicon, aluminum, boron, zinc, cobalt, or iron; Z comprises tungsten, molybdenum, niobium, or a combination thereof; MP⁺ is at least one d- or f-block element; v is from 1 to 9, and w is greater than or equal to 4.

In a more specific embodiment, when the polyoxometalate has the formula 1, the polyoxometalate has the formula [YV_(x)Z_(12−x)O₄₀[A], wherein Y is phosphorus, silicon, or aluminum; Z is tungsten or molybdenum; x is from 1 to 6, and A is a counterion. In one embodiment, Y is phosphorus and Z is molybdenum. In one embodiment, Y is phosphorus and Z is tungsten. In one embodiment, Y is silicon and Z is molybdenum. In one embodiment, Y is silicon and Z is tungsten. In one embodiment, Y is aluminum and Z is tungsten. In one embodiment, Y is aluminum and Z is molybdenum.

Polyoxometalates having an organic group, such as an alkyl group or aryl group, an organosilyl group, or other p- or d-block organometallic groups bonded to the POM can also be used in the present invention. The organic group can be branched or straight chain alkyl, alkenyl, or akynyl group or an aryl group of C₁ to C₃₀. The alkyl group can also be a polyether or polyol. Not wishing to be bound by theory, the organic group is bonded to the polyoxometalate as depicted in Scheme 1, where R is the organic group and Met is generally vanadium, molybdenum, tungsten, niobium, or tantalum:

The reaction between an alcohol and the polyoxometalate I results in the loss of water and the formation of the polyoxometalate II, wherein the organic group is bonded to an oxygen atom of the polyoxometalate. Any alcohol known in the art can be used in the present invention. Examples of alcohols that can be used include, but are not limited to, methanol, ethanol, or tris(hydroxymethyl)methane. The polyoxometalates having organic groups bonded to the POM that are disclosed in Gouzerh et al., Chem. Rev., 98, pp. 77–111, 1998, which is incorporated by reference in its entirety, are useful in the present invention.

In another embodiment, the polyoxometalate I can be reacted with a compound having the generic formula YL_(o)R_(4−o), wherein Y is silicon, tin, or an other p- or d-block element; L is a leaving group; R is an organic group, such as an alkyl, alkenyl, or alkynyl group of an aryl group of C₁ to C₃₀, and o is from 1 to 4. Suitable leaving groups for L include, but are not limited to, halides and alkoxides. In Scheme I, the oxygen of polyoxometalate I displaces L from YLR₃ to form a new Y—O bond (compound III). Any silyl, tin, or organic derivative of a p- or d-block element known in the art can be used in the present invention, provided that the compound has at least one leaving group.

The counterion A can be any counterion known in the art. Examples of counterions include, but are not limited to, quaternary ammonium cation, proton, alkali metal cation, alkaline earth metal cation, ammonium cation, d-block cations, f-block cations, or a combination thereof. In one embodiment, the polyoxometalate is an acid, wherein the counterion A is hydrogen (H⁺). In one embodiment, the counterion is a d- or f-block metal complex. In one embodiment, the counterion is trimethyl-triazacyclononane manganese. In another embodiment, the counterion A is hydrogen, lithium (Li⁺), sodium (Na⁺), potassium (K⁺), or a combination thereof. In another embodiment, A is not hydrogen or potassium.

In another embodiment, the polyoxometalate comprises a modified polyoxometalate, wberein the modified polyoxometalate comprises the admixture of (1) a pre-modified polyoxometalate and (2) a cerium compound, a silver compound, a gold compound, a platinum compound, a copper compound, a cobalt compound, or a combination thereof. The term “admixture” can refer to the reaction product between the polyoxometalate and the cerium compound, silver compound, gold compound, platinum compound, or a combination thereof. For example, the cerium compound, silver compound, gold compound, or platinum compound can undergo ion exchange with the counterion of the polyoxometalate. The cerium compound, silver compound, gold compound, or platinum compound can also react with the polyoxometalate by a redox reaction. The term “admixture” can also refer to when the cerium compound, silver compound, gold compound, or platinum compound do not react at all with the polyoxometalate. For example, the polyoxometalate may absorb the cerium compound, silver compound, gold compound, or platinum compound.

In one embodiment, when the POM is the sodium, lithium, or potassium salt or the acid form (A is H⁺), the POM can undergo ion exchange with a cerium compound, a silver compound, a gold compound, a platinum compound, or a combination thereof For example, Ag₅PV₂Mo₁₀O₄₀ is produced by the ion exchange of Na₅PV₂Mo₁₀O₄₀ with a stoichiometric amount AgNO₃. Any of the POMs described above can undergo ion exchange with a cerium compound, a silver compound, a gold compound, a platinum compound.

Depending upon the type and amounts of POM and cerium compound, silver compound, gold compound, or platinum compound used, the ion exchange reaction may or may not go to completion. When the ion exchange does not go to completion, there may be small population of Na⁺, Li⁺, K⁺, or H⁺ in the modified-polyoxometalate. For example, when H₅PV₂Mo₁₀O₄₀ is admixed with AgNO₃, the resultant POM may be expressed by the formula Ag_(x)H_(5−x)PV₂Mo₁₀O₄₀, where x is from 1 to 5. Here, varying amounts of H⁺ may be present in the POM.

An example of a cerium compound useful in the present invention includes, but is not limited to, (NH₄)₂Ce(No₃)₆. Examples of silver compounds useful in the present invention include, but are not limited to, AgNO₃ and AgClO₄. Examples of gold compounds useful in the present invention include, but are not limited to, HAuCl₄ and salts thereof. An example of a platinum compound useful in the present invention includes, but is not limited to, H₂PtCl₆.

In one embodiment, the counterion is cerium, silver, gold, platinum, or a combination thereof. In another enbodiment, A is, independently, cerium, silver, gold, or platinum. In another embodiment, A is (1) cerium and silver, (2) cerium and platinum; (3) cerium and gold; or (4) silver and gold.

In another embodiment, A comprises (1) hydrogen, lithium, sodium, potassium, or a combination thereof, and (2) cerium, silver, gold, platinum, or a combination thereof.

In one embodiment, (1) the pre-modified polyoxometalate is H₅PV₂Mo₁₀O₄₀, Na₅PV₂Mo₁₀O₄₀, Li₅PV₂Mo₁₀O₄₀, K₅PV₂Mo₁₀O₄₀, or a combination thereof, and (2) the cerium compound is (NH₄)₂Ce(NO₃)₆ In another embodiment, (1) the pre-modified polyoxometalate is H₅PV₂Mo₁₀O₄₀, Na₅PV₂Mo₁₀O₄₀; Li₅PV₂Mo₁₀O₄₀; K₅PV₂Mo₁₀O₄₀, or a combination thereof; (2) the cerium compound is (NH₄)₂Ce(NO₃)₆, and (3) the gold compound is HAuCl₄. In another embodiment, (1) the pre-modified polyoxometalate is H₅PV₂Mo₁₀O₄₀, Na₅PV₂Mo₁₀O₄₀, Li₅PV₂Mo₁₀O₄₀; K₅PV₂Mo₁₀O₄₀, or a combination thereof; (2) the cerium compound is (NH₄)₂Ce(NO₃)₆; and (3) the platinum compound is H₂PtCl₆. In another embodiment, (1) the pre-modified polyoxometalate comprises Na₄PVMo₁₁O₄₀; Na₅PV₂Mo₁₀O₄₀, Na₆PV₃Mo₉O₄₀; Na₅H₂PV₄W₈O₄₀, Na₉PV₆Mo₆O₄₀, Na₅CuPW₁₁O₃₉; Na₅CuPW₁₁O₃₉; Na₅MnPW₁₁O₃₉; K₅CoPW₁₁O₃₉; (n-Dec₄) ₆HMnNb₃P₂W₁₅O₆₂; or K₁₂Cu₃(W₉PO₃₄)₂, and (2) the gold compound is HAuCl₄ In another embodiment, (1) the pre-modified polyoxometalate is Na₅PV₂Mo₁₀O₄₀ and (2) the silver compound is AgNO₃, AgClO₄, or a combination thereof.

In another embodiment, the polyoxometalate comprises K₈Co₂W₁₁O₃₉; K₈SiCoVW₁₀O₃₉; K₇SiCoVW₁₀O₃₉, Na₈Co₂W₁₁O₃₉, Ag₅PV₂Mo₁₀O₄₀; Ag₆PV₃Mo₉O₄₀, Ag₈CoVW₁₁O₄₀; Ag₁₂Ce(PW₁₁O₃₉)₂, Na₁₂Ce(PW₁₁O₃₉)₂; K₁₂Ce(PW₁₁O₃₉)₂; Na₅PCuW₁₁O₃₉; H₆PV₃Mo₉O₄₀, or K₅Cu^(II)PW₁₁O₃₀. In another embodiment, the polyoxometalate is not H₆PV₃Mo₉O₄₀.

Not wishing to be bound by theory, it is believed that some counterions of the present invention can be reduced to the corresponding metal when the polyoxometalate contacts the contaminant. For example, when the cation is Ag⁺¹ or Au⁺³, these cations can be reduced to silver metal or Au⁺¹, respectively, depending upon the contaminant that is to be removed. Thus, the counterion A can exist in multiple valence states.

The phrase “metal compound” refers to one or more transition metal compounds, actinide compounds, lanthanide compounds, or a conbination thereof When the metal compound is only one compound, then the material is directly treated with the metal compound using techniques described below. When the metal compound is composed of two or more compounds, the material can be sequentially treated with the compounds, or alternatively, the metal compounds can be admixed prior to treating the material with the metal compounds. Depending upon the metal compounds that are selected, the metal compounds may react with one another to form a new species, or they may not react at all with each other to produce a composition or mixture. Materials that contain a metal compound of the present invention are referred to herein as “non-POM materials.”

In one embodiment, the metal compound comprises a cerium compound, a gold compound, a platinum compound, a silver compound, or a combination thereof. Any of the cerium compounds, gold compounds, platinum compounds, or silver compounds listed above can be used as the metal compound. In another embodiment, the metal compound is a cerium compound and a platinum compound, preferably (NH₄)₂Ce(NO₃)₆ and H₂PtCl₆, respectively. In another embodiment, the metal compound is a cerium compound and a gold compound, preferably (NH₄)₂Ce(NO₃)₆ and HAuCl₄, respectively. In another embodiment, the metal compound is a silver compound and a gold compound, preferably AgNO₃ and/or AgClO₄ and HAuCl₄, respectively. In another embodiment, the metal compound is a cerium compounds, preferably (NH₄)₂Ce(NO₃)₆.

In another embodiment, the metal compound comprises (1) gold, copper, and nitrate; (2) gold, iron, and nitrate; (3) gold, manganese, and nitrate; (4) gold, titanium, and nitrate; (5) gold, cobalt, and nitrate, (6) gold and nitrate, (7) copper and nitrate, (8) iron and nitrate; (9) gold, vanadium and nitrate; (10) gold, nickel, and nitrate, (11) gold, silver, and nitrate; or (12) gold, chloride, and nitrate. In a preferred embodiment, the metal compound comprises gold, chloride, and nitrate. In another embodiment, the metal compound comprises mixing (NEt₄)AuCl₂ with varying amounts of CuSO₄, MnSO₄, VOSO₁, Ti(SO₄)₂, Fe₂(SO₄)₃, NiSO₄, ZnSO₄, Cr₂(SO₄)₃, MgSO₄, CoSO₄, Pd(NO₃)₄, Na₂SO₃, and/or NBu₄NO₃. In another embodiment, the metal compound is produced by mixing (NEt₄)AuBr₂ and NBu₄NO₃.

When the metal compound comprises two or more compounds, the compounds can be admixed using techniques known in the art. In one embodiment, the metal compound can be produced by admixing two or more metal salts. The anion of the salt can be any anion known in the art. Examples of anions include, but are not limited to, sulfate, carbonate, acetate, nitrate, chloride, and stearate. In one embodiment, when two or more compounds are used to produce the metal compound, the compounds are mixed in the presence of a solvent, preferably an organic solvent. In one embodiment, After the compounds have been sufficiently admixed, the solvent is removed; and the metal compound is optionally dried. In one embodiment, the drying step is by vacuum.

Any POM or metal compound of the present invention can be incorporated into a material in order to remove a contaminant from the environment. Examples of materials include, but are not limited to, a topical carrier, a coating, a powder, or a fabric. As described above, a material as used herein refers to a support that holds the POM or metal compound.

In one embodiment, the polyoxometalate and the metal compound can be incorporated sequentially into the material. In one embodiment, the polyoxometalate is incorporated into the material followed by the incorporation of the metal compound into the material. In another embodiment, the metal compound is incorporated into the material followed by the incorporation of the polyoxometalate into the material.

A wide variety of topical carriers can be used in the present invention. Suitable topically acceptable pharmaceutical carriers are those which typically are used in the topical application of pharmaceuticals and cosmetics. Examples of such carriers include, but are not limited to, lotions, creams, ointments, and gels. Topical carriers are also referred to in the art as barrier creams and topical skin protectants. Any of the topical carriers disclosed in U.S. Pat. No. 5,607,979 to McCreery can be used in the present invention, which is incorporated by reference in its entirety. In one embodiment, the topical carrier comprises a perfluorinated polymer. In another embodiment, the topical carrier comprises a perfluoropolyether. An example of a perfluoropolyether (PFPE) useful in the present invention has the general formula CF₃O[—CF(CF₃)(CF₂O—]_(x)(—CF₂O—)_(y)CF₃). In one embodiment, the topical carrier comprises a perfluorinated polymer and one or more unfluorinated polymers. In another embodiment, the topical carrier comprises a perfluoropolyether and one or more unfluorinated polyethers.

In one embodiment, the topical carrier may further contain saturated or unsaturated fatty acids such as stearic acid, palmitic acid, oleic acid, palmito-oleic acid, cetyl or oleyl alcohols, stearic acid, fluorinated acids, fluorinated alcohols (e.g., tetrafluoroethanol), or combinations thereof. The cream may also optionally contain one or more surfactants, such as a non-ionic surfactant.

In one embodiment, the polyoxometalate topical composition is composed of a perfluoropolyether and the counterion A of the POM is silver. In another embodiment, the polyoxometalate topical composition is composed of a perfluoropolyether and the metal compound is a silver compound, a gold compound, or a combination thereof. In another embodiment, the non-POM material comprises a topical carrier composed of a perfluoropolyether and the metal compound comprises a silver compound, preferably AgNO₃ or AgClO₁.

In another embodiment, the non-POM topical composition is composed a perfluoropolyether and the metal compound comprises a cerium compound, a silver compound, a paladium compound, a platinum compound, or a silver compound.

A wide variety of powders and coatings known in the art can be used as the material of the present invention. In one embodiment, the powder comprises activated carbon.

Any fabric known in the art can be used to produce a polyoxometalate fabric or non-POM fabric of the present invention. In one embodiment, fabrics used to prepare garments, draperies, carpets, and upholstery can be used and articles made from them are a part of this invention. In another embodiment, the fabric can be a knit or non-woven fabric. Useful fibers include, but are not limited to, polyamide, cotton, polyacrylic, polyacrylonitrile, polyester, polyvinylidine, polyolefin, polyurethane, polytetrafluoroethylene, or carbon cloth, or a combination thereof. In one embodiment, the fabric is prepared from cotton, polyacrylic, or polyacrylonitrile. In one embodiment, the fabric is prepared from a cationic fiber. In another embodiment, the fabric comprises (1) a 50/50 blend of nylon-6,6 and cotton or (2) stretchable carbon blended with polyurethane.

Any cellulosic fiber can be incorporated by a POM or metal compound to produce the polyoxometalate fibers or non-POM fibers of the present invention. Examples of useful cellulosic fibers include, but are not limited to, wood or paper In a preferred embodiment, a polyoxometalate or the metal compound of the present invention can be incorporated in paper in order to remove a contaminant from the gas or liquid phase. In one embodiment, the paper is wallpaper.

The amount of polyoxometalate or metal compound incorporated into the material varies depending upon the contaminant to be removed and the material that is selected. There is no restriction on the amount of POM or metal compound that can be incorporated into the material. In one embodiment, the amount of polyoxometalate or metal compound incorporated in the material is from 0 1 to 95% by weight of the polyoxometalate material or non-POM material in one embodiment, the lower limit of polyoxometatate or metal compound by weight is 0.1, 0 5, 1 0, 2 0, 5 0, 10, 15, 20, 25, 30, 35, 40, 45, or 50%, and the upper limit is 30, 40, 50, 60, 70, 80, 90, or 95% in one embodiment, when the material is a topical carrier, the polyoxometalate or metal compound is from 5 to 30% by weight of topical composition.

The present invention is capable of removing a single contaminant or multiple contaminants from an environment. The term “environment” as used herein refers to any media that contains at least one contaminant. In one embodiment, the environment comprises a liquid phase. In another embodiment, the environment comprises a gas phase.

The term “remove” refers to, but is not limited to, the degradation of the contaminant, the conversion of the contaminant into another compound that is either less toxic or nontoxic and/or malodorous, or the adsorption of the contaminant by the polyoxometalate or the metal compound. The POM and metal compound can degrade the contaminant by a number of different mechanisms. For example, the POM can aerobically oxidize the contaminant acetaldehyde (CH₃CHO). Not wishing to be bound by theory, it is believed that the aerobic oxidation of CH₃CHO proceeds by a radical chain mechanism (i.e., the initiation of the radical chain by CH₃CHO+POM_(ox)→CH₃CO·+HPOM_(red)).

Contaminants that can be removed by using the present invention include, but are not limited to, an aldehyde, an aliphatic nitrogen compound, a sulfur compound, an aliphatic oxygenated compound, a halogenated compound, an organophosphate compound, a phosphonothioate compound, a phosphorothioate compound, an arsenic compound, a chloroethyl-amine compound, a phosgene compound, a cyanic compound, or a combination thereof. In one enbodiment, the contaminant is acetaldehyde, methyl mercaptan, ammonia, hydrogen sulfide, methyl sulfide, diethyl sulfide, diethyl disulfide, dimethyl sulfide, dimethyl disulfide, trimethylamine, styrene, propionic acid, n-butyric acid, n-valeric acid, iso-valeric acid, pyridine, formaldehyde, 2-chloroethyl ethyl sulfide, carbon monoxide, or a combination thereof. In another embodiment, the polyoxometalate materials and non-polyoxometalate materials can remove microbial life from the gas or liquid phase Examples of microbial life include, but are not limited to, bacteria, protozoa, and viruses.

In another embodiment, the contaminant is a chemical warfare agent (CW_(A)) The chemical warfare agents disclosed in Marrs, Timothy C., Maynard, Robert L. Sidell, Frederick R., Chemical Warfare Agents Toxicology and Treatment, John Wiley & Sons Chichester, England, 1996; Compton, James A. F Military Chemical and Biological Agents Chemical and Toxicological Properties; The Telford Press Caldwell, N.J., 1988; Somani, Satu M. Chemical Warfare Agents; Academic Press: San Diego, 1992, which are herein incorporated by reference in their entirety, can be removed by the polyoxometalate materials of the present invention.

The present invention can remove a contaminant from the environment in the gas phase under mild conditions. In one embodiment, the contaminant can be removed from −50° C. to 250° C. at a pressure of from 0.1 ppb to 30 atm, preferably from 25° C. to 105° C. at 1 atm. In another embodiment, the lower temperature limit is −50, −40, −30, −20, −10, 0, 10, 20, 50, 75, 100, or 150° C., and the upper temperature limit is 50, 75, 100, 125, 150, 175, 200, 225, or 250° C. In a preferred embodiment, the present invention can remove a contaminant from the environment at room temperature (approximately 25° C.) and at 1 atm. In another embodiment, the present invention can remove a contaminant from the gas phase that has a partial pressure of from 0.1 ppb to 2 atm, 10 ppb to 2 atm, 100 ppb to 2 atm, 200 ppb to 2 atm, and 0.5 ppm to 2 atm. Similarly, the present invention can remove a contaminant under mild conditions when the environment is a liquid phase. In one embodiment, the contaminant can be removed from a liquid media at from 0° C. to 200° C. The temperature depends upon the liquid media that is being contacted and the contaminant to be removed.

The POMs and metal compounds are typically used in the presence of an oxidizer to remove a containmant from the environment. In one embodiment, the POMs and/or metal compounds are used in the presence of air, which oxidizes the POM and/or metal compound. In another embodiment, additional oxidizers can be used in combination with air to oxidize the POM and/or metal compound. Examples of oxidizers include, but are not limited to, peroxides and peracids. In a preferred embodiment, air is used as the oxidizer.

The environment containing the contaminant can be contacted by the polyoxometalate materials or non-POM materials using a variety of techniques. For example, when the contaminant is in the liquid phase, the polyoxometalate material or non-POM material can be dipped or submersed into the liquid phase. Alternatively, the liquid phase can be filtered or passed through the polyoxometalate material or non-POM material. When the contaminant is in the gas phase, the polyoxometalate material or non-POM material is typically placed in an open or closed environment that contains the contaminant(s).

The polyoxometalate materials or non-POM materials of the present invention have a number of advantages over the prior art materials that do not use a polyoxometalate to remove a contaminant from the environment. One advantage is that the present invention can remove a contaminant from the environment starting within milliseconds of contact and can remove the contaminant for extended periods of time, ranging from several days to indefinitely. The POMs and metal compounds used in the present invention are capable of being regenerated to an active form that permits the removal of the contaminant. Another advantage is that some POMs and metal compounds can render the material more water resistant and increase the surface area of the material. Finally, when the material is a fabric or cellulosic fiber, the POM and metal compound can enhance the dyeability, light fastness, color fastness, and weaving properties of the fabric or cellulosic fiber.

The polyoxometalate and metal compound can be incorporated into the material using techniques known in the art. In one embodiment, when the material is a topical carrier, powder, or coating, the polyoxometalate or metal compound is directly added to and admixed with the material. In another embodiment, the material (topical carrier, powder, coating, or fabric) is contacted with a mixture comprising the polyoxometalate or metal compound and a solvent. The polyoxometalate or metal compound can be soluble, partially soluble, or insoluble in the solvent, depending upon the polyoxometalate or metal compound and solvent selected in one embodiment, the solvent is water. In another embodiment, the solvent can be an organic solvent Examples of organic solvents useful in the present invention include, but are not limited to, acetonitrile, acetone, toluene, carbon dioxide, xylenes, 1-methyl-2-pyrrolidinone, dimethyl sulfoxide, or an alcohol, such as methanol ethanol, 1-propanol or 2-propanol.

In one embodiment, when the material is a fabric or cellulosic fiber, the polyoxometalate or metal compound mixture is from 0.1 to 20% by weight polyoxometalate or metal compound and from 80 to 99.9% by weight water, preferably from 0.3 to 15% by weight polyoxometalate or metal compound and 85 to 99 7% water. Generally, the fabric or cellulosic fiber is dipped or immersed into the mixture containing the POM or metal compound for several hours to days at a temperature of from 0° C. to 100° C., preferably for 2 hours to 2 days at from 25° C. to 80° C. in another embodiment, the POM or metal compound can be admixed with a resin or adhesive, and the resultant adhesive is applied to the surface of or admixed with the fabric or cellulosic fiber.

Typically, once the material has been contacted with the POM or metal compound mixture, the polyoxometalate material or non-POM material is dried in order to remove residual solvent. In one embodiment, the polyoxometalate materials or non-POM material is heated from 0° C. to 220° C. at or below atmospheric pressure, preferably from 25° C. to 100° C. In another embodiment, the polyoxometalate material or non-POM material ts dried in vacuo (i.e., less than or equal to 10 torr)

In another embodiment, when the material is a fabric or cellulosic fiber, the POM or metal compound can be incorporated into the fabric or cellulosic fiber by depositing the POM or metal compound on the surface of an existing fabric or cellulosic fiber, covalently bonding the POM or metal compound to the fibers of the fabric or cellulosic fiber, impregnating or intimately mixing the POM or metal compound with the fabric or cellulosic fiber, electrostatically bonding the POM or metal compound to the fabric or cellulosic fiber, or datively bonding the POM or metal compound to the fabric or cellulosic fiber via the coordination of a d- or f- block metal ion on the surface or the POM or metal compound with a functional group on the fabric. In the case of electrostatically bonding the POM to the fabric or cellulosic fiber, the positively charged functional groups on the fabric or cellulosic fiber and the negatively charged POM can form an electrostatic bond. In one embodiment, when the counterion of the polyoxometalate is a proton or the metal compound is an acid, the fabric or cellulosic fiber can be protonated by the polyoxometalate or metal compound to produce a positively charged fiber, which then electrostatically bonds to the polyoxometalate or metal compound anion. In one embodiment, a cationc polymer can be used as a binding agent to incorporate an anionic polyoxometalate or metal compound into an anionic fiber.

EXAMPLES

The following examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how the compositions, materials, and methods claimed herein are made and evaluated, and are intended to be purely exemplary of the invention and are not intended to limit the scope of what the inventors regard as their invention. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.) but some errors and deviations should be accounted for. Unless indicated otherwise, parts are parts by weight, target odorants/toxics are expressed in parts per million, temperature is in ° C. or is at ambient temperature and pressure is at or near atmospheric.

The term “consumption” or “consumed” refers to the removal or adsorption of a contaminant or contaminants from the environment or the conversion of the contaminant or contaminants to another compound that is nontoxic and/or non-malodorous.

General Considerations

Materials. PFPE #1511 is composed of 35–50% polytetrafluoroethylene thickening agent dispersed in a perfluoropolyether oil with water as a co-surfactant PFPE #1511 was provided by Dr. E. H. Braue of the United States Army Medical Research Institute for Cheuical Defense.

All reagents used in the examples were obtained from Aldrich Chemical Company, Milwaukee, Wis., and were used without further purication. The following reagents were used in the examples (the purity of the reagent is in parenthesis) CEES (98%), HPLC grade acetonitrile, tetrafluorethylene (99.5%), 1,3-dichlorobenzene (98%), dimethyl sulfoxide (DMSO) (99.8%), AgNO₃ (99+%), HAuCl₄ (99+%), CuCl₂ (99+%), FeCl₃ (98%), AgClO₄ (99 9%), (NEt₄)AuCl₂, CuSO₄(99.99%), MnSO₄ (98%), VOSO₄ (99 99%), Ti(SO₄)₂ (99%), Fe(SO₄)₃ (97%), NiSO₄ (99%), ZnSO₄ (99%), Cr₂(SO₄)₃ (99.999%), MgSO₄ (99%), CoSO₄ (99 998%), Pd(NO₃)₄ (98%), Na₂SO₃ (99%), and NBu₄NO₃ (97%). NBu₄NO₂ (98%) was purchased from Fluka.

Synthesis of Ag_(x)Na_(5−x)PV₂Mo₁₀O₄₀

Na₅PV₂Mo₁₀O₄₀ was prepared by the literature procedure outlined in Petterson, L., Andersson, I., Selling, A; Grate, J. H Inorg. Chem 1994, 33, 982. Ag_(x)Na_(5−x)PV₂Mo₁₀O₄₀ was prepared using the following procedure. Ground H₅PV₃Mo₁₀O₄₀ (30.9 g, 1.78×10⁻² mol) was dissolved in 200 mL of distilled water The orange solution was filtered three times to remove any undissolved POM Ground AgNO₃ (15 2 g, 8.94×10⁻² mol) was added with vigorous stirring. The mixture was stirred overnight at room temperature. The product precipitated as a dark red-orange powder and was removed by suction filtration over a medium fritted glass funnel The product was dried in vacuo overnight. The IR spectrum of the resultant powder confirmed the formation of Ag_(x)Na_(5−x)PV₂Mo₁₀O₄₀.

Synthesis of Additional Polyoxmetalates

The following POMs listed in Table 8 were prepared by literature procedures (the entry number in Table 8 and the bibliographical information are in parenthesis)

-   Na₅CuPW₁₁O₃₉; Na₅MnPW₁₁O₃₉; K₅MnPW₁₁O₃₉; and K₅CoPW₁₁O₃₉: (Entries     2–4 and, 6, respectively; Maksimov, G. M.; Kustova, G. N.;     Matveev, K. I., Lazarenko, T P Koord. Khim. 1989, 15(6), 788–96). -   Na₅PV₂Mo₁₀O₄₀ and H₅PV₂Mo₁₀O₄₀: (Entries 7 and 20, respectively;     O'Donnell, Stephen E.; Pope, Michael T. J. Chem. Soc., Dalton Trans.     1976, 21, 2290–7). -   Na₄PVMo₁₁O₄₀. (Entry 11; So, Hyunsoo; Pope, Michael T Inorg. Chem.     1972, 11(6), 1441–3). -   Na₆PV₃Mo₉O₄₀ and H₆PV₃Mo₉O₄₀ (Entries 8 and 21, respectively; Pope,     Michael T, O'Donnell, Stephen E.; Prados, Ronald A. J. Chem. Soc.,     Chem. Commun. 1975, 1, 22–3). -   Na₅H₂PV₄Mo₈O₄₀ and H₇PV₄Mo₈O₄₀: (Entries 9 and 22, respectively,     Yurchenko, E N J. Mol. Struct. 1980, 60, 325–31). -   Na₅FeSiW₁₁O₃₉ and K₆FeSiW₁₁O₃₉: (Entries 12 and 36, respectively;     Peacock, R D Weakley, T J R. J. Chem. Soc. A 1971, 12, 1937–400). -   Na₅SiVW₁₁O₄₀: (Entry 13, Tourne, Claude; Tourne, Gilbert. Bull. Soc.     Chim. Fr. 1969, 4, 1124–36). -   K₈Co(II)P₂W₁₇O₆₁: (Entry 15; Marcu, Gheorghe; Patrut, Adrian; Botar,     Alexandru, Rev. Chim. (Bucharest) 1989, 40(11), 870–5). -   K₁₂Pd₃(PW₉O₃₄)₂: (Entry 16; Kuznetsova, N. I.; Kuznetsova, L. I.;     Detusheva, L. G. Likholobov, V. A.; Fedotov, M. A; Koscheev, S. V.;     Burgina, E. B. Stud. Surf. Sci. Catal. 1997, 110 (3rd World Congress     on Oxidation Catalysis, 1997), 1203–1211). -   K₈Cu(II)P₂W₁₇O₆₁: (Entry 17; Hamlaoui, Mohamed Larbi; Vlassenko,     Konstantin, Messadi, Djelloul C. R. l'Academie Sci, Ser. II Univers     1990, 311(7), 795–8). -   Na₄PVMo₁₁O₄₀ and Na₃PMo₁₂O₄₀: (Entries 18 and 19, respectively; So,     Hyunsoo, Pope, Michael T. Inorg. Chem. 1972, 11(6), 1441–3). -   Na₁₆P₄W₃₀Cu₄O₁₁₂: (Entry 24; Huang, Ru-Dan; Bei Bao-Li; Wang, En-Bo;     Li, Bai-Tao; Zhang, Su-Xia. Gaodeng Xuexiao Huaxue Xuebao 1998,     19(11), 1721–1723). -   K₁₀Ce(PW₁₁O₃₉)₂. (Entry 26, Peacock, R. D ; Weakley, T J. R J. Chem.     Soc. A 1971, 12, 1937–40). -   K₇CuSiW₁₁O₃₉ and Na₇CuSiW₁₁O₃₉. (Entries 27 and 30, respectively;     Teze, Andre; Souchay, Pierre. C. R. Acad. Sci., Ser. C 1973,     276(19), 1525–8) -   Na₅NiPW₁₁O₃₉. (Entry 31, Maksimov, G M.; Kustova, G. N., Matveev, K.     I.; Lazarenko, T. P Koord. Khim. 1989, 15(6), 788–96). -   Na₃AsW₁₂O₄₀: (Entry 35; Tsyganok, L. P, Statsenko, V P., Vil'dt,     A L. Zh. Neorg Khim. 1974, 19(11), 3071–7). -   K₈NiP₂W₁₇O₆₁: (Entry 37; Hamlaoui, Mohamd Larbi; Vlassenko,     Konstantin; Messadi, Djelloul. C. R. l'Academie Sci., Ser. II     Univers 1990, 311(7), 795–8). -   (Me₄N)₁₀(Co₃SiW₉O₄₀H₆): (Entry 38; Nomiya, Kenji; Miwa, Makoto.     Polyhedron 1985, 4(8), 1407–12). -   Na₃V₁₀O₂₈: (Entry 40; Preuss, F.; Rosenhahn, L. J. Inorg. Nucl.     Chem. 1972, 34(5), 1691–703). -   K₈P₂W₁₇(NbO₂)O₆₁: (Entry 42; Gong, Jian; L, Guoping; Wang, Fuquan;     Qu, Lunyu Wuji Huaxue Xuebao 1995, 11(3), 232–7). -   (NH₄)₆P₂FeW₁₇O₆₁: (Entry 43; Peacock, R. D.; Weakley, T. J. R. J.     Chem. Soc. A 1971. Issue 12, 1937–40). -   K₇Mn(II)P₂W₁₇O₆₁: (Entry 44; Marcu, Gheorghe; Patrut, Adrian; Botar,     Alexandru (1). Rev. Chim. (Bucharest) 1989, 40(11), 870–5). -   (NH₄)₆P₂W₁₈O₆₂. (Entry 50; Varga, Gideon M, Jr, Papaconstantinou,     Elias, Pope, Michael T Inorg. Chem. 1970, 9(3), 662–7) -   Na₉PV₆Mo₆O₄₀: (Entry 1, Ret'yakov, V P.; Volkova, L K; Zimtseva, G.     P, Rudakov, E, S. Kinet. Katal. 1993, 34(1), 183). -   K₁₂Cu₃(W₉PO₃₄)₂. (Entry 10; Weakley, Timothy J. R., Finke, Richard G     Inorg. Chem. 1990, 29(6), 1235–41) -   K(NH₄)₆RuBW₁₁O₃₉: (Entry 34; Liu, Huizhang; Sun, Wenliang; Yue, Bin;     Li, Mingxing; Chen, Zhijiang; Jin, Songlin; Xie, Gaoyang; Shao,     Qianfen, Wu, Tailiu, Chen, Shimmg; Yan, Xiaoming. Wuji Huaxue Xuebao     1997, 13(3), 251–257). -   K₁₀Ni₄P₂W₁₇O₆₁: (Entry 14; Yon, David K; Miller, Warren K; Novet,     Thomas; Domaille, Peter J., Evitt, Eric; Johnson, David C.; Finke,     Richard G. J. Am. Chem. Soc. 1991, 113(19), 7209–21). -   K₁₀Co₄P₂W₁₈O₆₈: (Entry 39; Evans, Howard T.; Tourne, Claude M.;     Tourne, Gilbert F., Weakley, Timothy J. R. J. Chem. Soc., Dalton     Trans. 1986, 12, 2699–705). -   K10Mn4(PW₉O₃₄)₂: (Entry 41; Gomez-Garcia, C. J.; Coronado, E.;     Gomez-Romero, P, Casan-Pastor, N. Inorg. Chem. 1993, 32(15),     3378–81). -   K₁₀Cu₄P₂W₁₈O₆₈: (Entry 45; Weakley, Timothy J. R; Finke, Richard G.     Inorg. Chem. 1990, 29(6), 1235–41). -   K₁₂P₂W₁₈Ni₃O₆₈: (Entry 47; Gomez-Garcia, Carlos J; Coronado,     Eugenio; Ouahab, Lahcene. Angew. Chem. 1992, 104(5), 660–2). -   Na₆P₄W₃₀Mn(II)₄O₁₁₂: (Entry 49; Gomez-Garcia, C. J.;     Borras-Almenar, J. J.; Coronado, E., Ouahab, L. Inorg. Chem. 1994,     33(18), 4016–22) -   K₈Co₂W₁₁O₃₉: (Entry 29; Walmsley, F. J Chem. Ed. 1992, 69(11),     936–38) -   (NH₄)₁₇Na(NaSb₉W₂₁)O₈₆. (Entry 51; Minami, N.; Hiraoka, M., Izumi,     K.; Uchida, Y Japanese Patent JP 08113731 A2 1996, Chem. Abstr.     1996, 125, 117542) -   Na₃H₃PMo₉O₃₄: (Entry 48, Inouye, Y., Tokutake, Y , Kunihara, J ,     Yoshida, T, Yamase, Y ; Nakata, A., Nakamura, S Chem. Pharm. Bull.     1992, 40, 805–807) -   K₈CoVW₁₁O₄₀ (Entry 28, Bas-Serra, J., Todorut, et al. Synth. React.     Inorg. Met. Org. Chem. 1995, 25(6), 869–82). -   H₂Na₁₄[Fe(III)₂(NaH₂O)₂(P₂W₁₅O₅₆)₂]: (Entry 25; Shigeta, S.; Mori,     S., Watanbe, J., Baba, M , Khenkin, A M.; Hill, C. L., Schmazi R. F.     Antiviral Chem. Chemother. 1996, 346–352). -   K₆SiTiW₁₁O₄₀: (Entry 33; Blasecki, J. W Top. Mol. Org. Eng. 1994,     10, 373–385) -   K₈Cu(II)P₂W₁₇O₆₁: (Entry 17; Marcu, Gheorghe; Patrut, Adrian; Botar,     Alexandru. Rev. Chim. (Bucharest) 1989, 40(11), 870–5). -   (n-Dec₄)₆HMnNb₃P₂W₁₅O₆₂. (Entry 5, Gong, J., Chen, et al.     Polyhedron, 1996, 15, 2273–7).     The following POMs were prepared by the following experimental     procedures.

K₅Si(NbO₂)W₁₁O₄₀ (Entry 46) 1 0 g of K₇HNb₆O₁₆ was dissolved in 75-mL of deionized H₂O. To this solution, 2-mL of 30% H₂O₂ was added. A few drops of 3M HCl were added to bring the pH to approximately 6. K₈SiW₁₁O₃₉ (15.8 g) was added. which resulted in gas evolution. To the swirling mixture, 25-ml of H₂O followed by 12-mL of 3M HCl were added. The color of the solution was yellow and the pH was approximately 1 The mixture was stirred for an additional 30 minutes, then 14 g of solid KCl was added, which resulted in the formation of a pale yellow solid. The solid was collected by filtration and dried resulting in 4.7 g of K₅Si(NbO₂)W₁₁O₄₀.

Na₆SiVNbW₁₁O₃₉ (Entry 32) 6 64 g of K₇Hb₆O₁₉ was dissolved in 800-mL of H₂O To this solution, 80-mL of 30% H₂O₂ solution was added and the pH was adjusted to 6.0 with KOH. Solid K₉StVW₁₀O₃₉ was added slowly to produce a final pH of 8 5. To this mixture, 40-mL of 3M HCl was added dropwise. The addition was stopped occasionally to agitate the solid. The solution was then stirred for 15 minutes Additional 3M HCl (40-mL) was added to give a pH of 1.5. The solution was stirred for 1 hour, and 160 g of solid KCl was added. The orange precipitate was filtered off and dried, yielding 40.85 g of K₆SiVNbW₁₁O₃₉. K₆SiVNbW₁₁O₃₉ and water were passed through an Amberlite IR-120 ion exchange column which was charged with 1 M NaCl. The volatiles were removed from the collected solution by vacuum to produce Na₆SiVNbW₁₁O₃₉ as a yellow, crystalline solid. The Amberlite is a product of Rohm and Haas and was purchased from Aldrich.

Instrumentation. Gas chromatography analysis was conducted using a Hewlett-Packard Series 5890 Gas Chromatograph equipped with a flame ionization detector and fitted with a non-polar 5% PHME siloxane, 30 meter column. Alternatively, the gas chromatograph was equipped with an FID detector and a 5% phenyl methyl silicone capillary column. Mass abundance determinations were performed using a HP 5890 GC with a 5% phenyl methyl silicone capillary column and a 5971A Mass Selective Detector. Gas chromatography/mass spectroscopy was performed using a Hewlett-Packard Series II 5890 Gas Chromatograph equipped with a 5971A mass selective detector and fitted with a non-polar 5% PHME siloxane, 25 meter column. For both GC and GC-MS, nitrogen was used as the carrier gas in Examples 5 and 6, all reactions were monitored using a Hewlett-Packard 6890 gas chromatograph with flame ionization detector and HP-5 (5% phenylethylsilicone capillary column. UV-visible spectra were run on a HP 8452A Diode Array Spectrophotometer The percentages of O₂ of the reaction atmosphere were vaned using a Series 810 Mass Trak flowmeter with dried argon as the other gas.

Example 1 Oxidation of CEES to CEESO by a POM/TSP Mixture under Ambient Conditions after 40 Days

PFPE #1511 (0.525 g) was combined with Ag_(x)Na_(5−x)PV₂Mo₁₀O₄₀ (0 066g, 3 81×10⁻⁵ mol) to give a 11% weight/weight POM/cream mixture The POM/cream mixture was placed in a 18 mL glass vial fitted with a poly(tetrafluoroethylene) (PTFE) stopper A sufficient amount of 2-chloroethyl ethyl sulfide (CEES) was added to the mixture to completely submerge the POM/cream mixture. After 40 days, 10 μL of the CEES solution surrounding the POM/cream mixture was removed and diluted into 100 μL of 2,2,2-trifluoroethanol (TFE). GC-MS of this solution showed the presence of 2-chloroethyl ethyl sulfoxide (CEESO).

Example 2 Oxidation of CEES to CEESO by POM/TSP Mixtures under Ambient Conditions

The CEES composition used in all trials was composed of 90 mL of CEES combined with 100 μL of 1,3-dichlorobenzene, where the 1,3-dichlorobenzene was added as an internal reference. Each POM/PFPE #1511 cream mixture (approximately 0 3 g) was smeared at the bottom of an 18 mL glass vial and fitted with a PTFE cap The CEES composition (1.0 mL) was then added and each vial was left undisturbed for several days under ambient conditions, with periodic GC analysis of the CEES/reference solution to check for CEESO formation. For GC analysis, 10 μL of the CEES/reference solution surrounding the POM/cream mixture was diluted in 100 μL of TFE and analyzed. The results are shown in Table 1.

TABLE 1 Weight Turnovers after Entry Catalyst Percent^(a) 9 Days^(b) 1 cream only N/A 0 2 AgNO₃ 20.3% 0 3 H₅PV₂Mo₁₀O₄₀  5.8% 0 4 H₅PV₂Mo₁₀O₄₀ 20.8% 0 5 Ag_(x)Na_(5−x)PV₂Mo₁₀O₄₀  5.6% 0 6 Ag_(x)Na_(5−x)PV₂Mo₁₀O₄₀ 20.6% 0 7 HAuCl₄  7.1% 0 8 HAuCl₄, AgNO_(3,)  7.6% 5 AgClO₄ ^(c) ^(a)Weight Percent = (mass of POM (g))/(mass of cream (g) + mass of POM (g)) × 100 ^(b)Turnovers = (mol of CEESO/mol of catalyst) × 100 ^(c)This mixture was composed of 1 equiv. of HAuCl₄, 1.25 equiv. of AgClO₄, and 0.75 equiv. of AgNO₃. The weight percent is reported as the (weight of all components, g)/(weight of cream, g + weight of components, g) × 100

Example 3 Catalytic Oxidation of CEES by POMs in 2,2,2-Trifluoroethanol after 14 Days under Ambient Conditions

A CEES solution was prepared by mixing 85.8 mM of CEES; 1.51×10⁻⁵ to 182×10⁻⁵ mol of catalyst; 100 μL 1,3-dichlorobenzene (internal standard); and 85 mL of 2,2,2-trifluoroethanol, at 25° C. under ambient air. In a typical run, 50 mL of the CEES solution was combined with enough catalyst to yield a CEES.POM ratio ot 20 1, and the mixture was stirred for 14 days. The results are shown in Table 2.

TABLE 2 Entry Catalyst CEESO Turnovers^(a) 1 AgNO₃ 0.42 2 Ag_(x)H_(5−x)PV₂Mo₁₀O₄₀ 8.13 3 Ag_(x)H_(4−x)PVMo₁₁O₄₀ 1.18 4 Na₅PV₂Mo₁₀O₄₀ 0.00 5 K₅CoVW₁₁O₄₀ 0.00 6 K₅Cu^(II)PW₁₁O₃₉ 15.33 7 Ag_(x)K_(12−x)Ce(PW₁₁O₃₉)₂ 4.47 8 (NH₄)₂Ce(NO₃)₆ 18.53 9 Ag_(x)K_(4−x)Cu^(II)PW₁₁O₃₉ 15.21 ^(a)Turnovers = (mol of CEESO/mol of catalyst) × 100

Example 4 Aerobic Oxidation of Acetaldehyde Catalyzed by Polyoxometalates

In a 20 mL vial 0.961 mmol acetaldehyde, 2 mg of POM, and pentane (internal standard) (34.7 μL) were stirred in 2 mL of chlorobenzene under 20 mL (0.82 mmol) of O₂ at 298 K for 24 hours. Under these conditions, the POM was totally insoluble at all times during the reaction. For the cloth samples, the polyoxometalate was deposited as a 5% by weight solution of H₂O and subsequently dried. BHT (2,6-di-tert-butyl-p-cresol) was used as a radical inhibitor in a 1 2 mol ratio versus POM. The aerobic oxidation of acetaldehyde by the POMs is shown in Table 3.

TABLE 3 Time Equivalents % Conversion of % Yield Entry Catalyst (h) CH₃CHO^(a) Acetaldehyde^(b) Acetic Acid^(c) Turnovers^(d) 1 Blank 24 — 8   0 — 2 Na₈Co₂W₁₁O₃₉ 24 1538 97.8 67.2 1033 3 K₈SiCoVW₁₀O₃₉ 24 1521 95.7 60.2 916 4 K₇SiCoVW₁₀O₃₉ 24 1483 92.3 55.8 827 5 Blank 28.5 — 37 10 — 6 Na₈Co₂W₁₁O₃₉ 28.5 3075 80.3 70.3 1844 7 K₈SiCoVW₁₀O₃₉ 28.5 3041 72.1 59.4 1491 7 K₇SiCoVW₁₀O₃₉ 28.5 2966 73.3 62.4 1545 8 Cotton-Na₈Co₂W₁₁O₃₉ 24 1538 98.2 66.2 815 9 Cotton-K₈SiCoVW₁₀O₃₉ 24 1521 90.4 50.0 644 10 1 Na₈Co₂W₁₁O₃₉/1.2 BHT 24 1538 17.8 22.4 180 ^(a)Equivalents of Acetaldehyde = moles of acetaldehyde (material)/moles of POM For the last three reactions (Entries 5–8) after 24 h another 0.961 mmol acetaldehyde was added, and the suspension was allowed to stir for an additional 8 h. All values are averages of two experiments. ^(b)% Conversion = (moles of acetaldehyde consumed/moles of initial acetaldehyde) × 100. ^(c)% Yield = (moles of acetic acid/moles of initial acetaldehyde) × 100. ^(d)Turnovers = [moles of acetic acid (in the run with catalyst) - moles of acetic acid (in the blank run without catalyst)]/moles of catalyst.

Example 5 Aerobic Oxidation of Tetrahydrothiophene in Liquid Phase by Modified Polyoxometalates and Metal Compounds

Tetrahydrothiophene (THT) (0.445 mmol 0.64 M) and 1,3-dichlorobenzene (internal standard) in the presence or absence of the polyoxometalate and/or metal compound were stirred in 4 mL of acetonitrile in 20 mL vials under 1 atm O₂ at room temperature. The aerobic oxidation of THT by modified polyoxometalates and metal compounds is shown in Table 4. In Entries 3–7 and 12, 2×10⁻⁴ mmol of polyoxometalate or metal compound was placed in the vial before adding the reagent and internal standard. In Entries 8–14, the polyoxometalate and metal compound (Entries 11 and 14)or the metal compounds were placed in the vial before the addition of the reagent and the internal standard. In Entries 8–14, 2×10⁻⁴ mol of each POM or metal compound was used in a 1/1 ratio.

TABLE 4 Entry Catalyst Time (h) Yield %^(a) Turnover^(b) 1 Blank^(c) 3.5 0 — 2 Blank^(c) 72^(d) 0 — 3 H₅PV₂Mo₁₀O₄₀ 3.5 0 0 4 HAuCl₄ 3.5 0 0 5 HAuCl₄ 72^(d) 0 0 6 (NH₄)₂Ce(NO₃)₆ 3.5 14 12 7 (NH₄)₂Ce(NO₃)₆ 72^(d) 26 100 8 (NH₄)₂Ce(NO₃)₆ + 3.5 14 12 H₅PV₂,Mo₁₀O₄₀ 9 (NH₄)₂Ce(NO₃)₆ + 3.5 67 57 HAuCl₄ 10 (NH₄)₂Ce(NO₃)₆ + 72^(d) 76 293 HAuCl₄ 11 (NH₄)₂Ce(NO₃)₆ + 3.5 65 56 HAuCl₄ + H₅PV₂Mo₁₀O₄₀ 12 H₂PtCl₆ 3 0 0 13 (NH₄)₂Ce(NO₃)₆ + 3 25 21 H₂PtCl₆ 14 (NH₄)₂Ce(NO₃)₆ + 3 26 23 H₂PtCl₆ + H₅PV₂,Mo₁₀O₄₀ ^(a)Moles of THTO/moles of initial THT. ^(b)Moles of THTO/moles of catalyst. ^(c)No catalysts. ^(d)More THT and O₂ added to the reaction system after 24 hr of initial reaction.

Example 6 Aerobic Oxidation of CEES in Liquid Phase by Modified Polyoxometalates and Metal Compounds

CEES (0 337 mmol, 0 64 M) and 1,3-dichlorobenzene (internal standard) in the presence or absence of the polyoxometalate and/or metal compound were stirred in 4 mL of acetonitrile in 20 mL vials under 1 atm of O₂ at room temperature. The aerobic oxidation of CEES by modified polyoxometalates and metal compounds is shown in Table 5. In Entries 2, 3, 5, and 6, 2×10⁻⁶ mol of polyoxometalate or metal compound was placed in the vial before adding the reagent. In Entries 4 and 7–12, the polyoxometalate and/or the metal compound(s) (2×10⁶ mol) were placed in the vial before adding the reagent solution.

TABLE 5 Time Conver- Turn- Entry Catalyst (day) sion %^(a) Yield %^(b) over^(c) 1 Blank^(d) 3 0 0 — 2 HAuCl₄ 3 0 0 0 3 H₅PV₂Mo₁₀O₄₀ 3 1 0 0 4 HAuCl₄ + H₅PV₂Mo₁₀O₄₀ 3 12 3 2 5 (NH₄)₂Ce(NO₃)₆ 1 16 8 5 6 (NH₄)₂Ce(NO₃)₆ 3 26 18 12 7 (NH₄)₂Ce(NO₃)₆ + HAuCl₄ 1 28 9 6 8 (NH₄)₂Ce(NO₃)₆ + HAuCl₄ 3 57 36 24 9 (NH₄)₂Ce(NO₃)₆ + 1 47 24 15 H₅PV₂Mo₁₀O₄₀ 10 (NH₄)₂Ce(NO₃)₆ + 3 64 41 27 H₅PV₂Mo₁₀O₄₀ 11 (NH₄)₂Ce(NO₃)₆ + HAuCl₄ + 1 53 43 28 H₅PV₂Mo₁₀O₄₀ 12 (NH₄)₂Ce(NO₃)₆ + HAuCl₄ + 3 82 70 46 H₅PV₂Mo₁₀O₄₀ ^(a)Moles at CEES consumed/moles of initial CEES. ^(b)Moles of CEESO (the GC response factor of CEESO is assumed the same as that of CEES)/moles of initial CEES. ^(c)Moles of CEESO (the GC response factor of CEESO is assumed the same as that of CEES)/moles of catalyst. ^(d)No catalyst.

Example 7 Aerobic Oxidation of CEES in Liquid Phase by a Polyoxometalate and HAuCl₄

Each POM (9 61×10⁶ mol); HAuCl₄ (4 8×10⁻⁵ mol); 1,3-dichlorobenzene (9.61×10⁻⁴ mol), and CEES (9 61×10⁻⁴ mol) were stirred in 4 mL of acetonitrile under 20 mL (0.82 mmol) of O₂ at 298 K. The aerobic oxidation is shown in Table 6

TABLE 6 Time Turnovers^(a) Time Turnovers^(a) Entry Catalyst (h) of CEESO (h) of CEESO 1 Na₄PVMo₁₁O₄₀ 4 0 11 1.1 2 Na₅PV₂Mo₁₀O₄₀ 4 5.0 11 10.6 3 Na₆PV₃Mo₉O₄₀ 4 7.0 11 18.3 4 Na₅H₂PV₄W₈O₄₀ 4 4.4 11 14.2 5 Na₉PV₆Mo₆O₄₀ 4 5.6 11 20.7 6 Na₅CuPW₁₁O₃₉ 4 59.2 11 83.6 7 HAuCl₄ 4 0 11 0 ^(a)Turnovers = (moles of CEESO (catalyst run) − moles of CEESO (blank run))/moles of catalyst.

Example 8 Aerobic Catalytic Oxidation of CEES to the Sulfoxide (CEESO) using AgNO_(y)/HAuCl₄ System (non-POM system)

A metal compound solution was prepared by combining AgNO₃ (1 0×10⁵ mol) and HAuCl₄ (5.0×10⁻⁶ mol) in 1 mL of acetonitrile. To this solution was added CEES (3.0×10⁻³ mol). Upon addition of CEES to the solution, a white precipitate immediately formed. The precipitate is believed to be a silver containing salt, possibly coordinated to CEES. The solution was allowed to stir for 100 hours, at which time there was loss of CEES in the solution based on gas chromatography. The filtrate was taken to dryness, and a solution containing excess CEES in acetonitrile was added to the yellow oily residue. Gas chromatography of the solution confirmed the formation of CEESO. The results are shown in Table 7 (entries 1–7).

Example 9 Aerobic Catalytic Oxidation of CEES to the Sulfoxide (CEESO) using AgNO₃/AgClO₄/HAuCl₄ System (non-POM system)

A 20 mL vial fitted with a PTFE septum was purged with 1 atm of O₂. To this vial were added by syringe, 0.035 mL of AgNO₃ (0.1013 M in acetonitrile); 0 060 mL of AgClO₄ (0.1138 M in acetonitrile); and 0.100 mL HAuCl₄ (0.0477 M in acetonitrile), and the total volume was adjusted to 1 mL with the addition of HPLC grade acetonitrile To this solution, 0.36 mL (2.86×10⁻³ mol) of CEES were added to the solution, and the formation of CEESO was monitored over time by gas chromatography using 1,3-dichlorobenzene as the internal reference. The results are summarized in Table 7 (Entries 8–11).

TABLE 7 Time Entry Catalyst (hrs) Turnover^(a) 1 2 AgNO₃ 100 0 2 2 AgClO₄ 100 0 3 1 HAuCl₄ 100 0.9 4 2 AgNO₃ + 1 HAuCl₄ 1 13.0 5 2 AgNO₃ + 1 HAuCl₄ 2 21.3 6 2 AgNO₃ + 1 HAuCl₄ 24 83.5 7 2 AgNO₃ + 1 HAuCl₄ 100 146.3 8 0.75 AgNO₃ + 1.25 AgCl₄ + 1 HAuCl₄ 1 38.3 9 0.75 AgNO₃ + 1.25 AgCl₄ + 1 HAuCl₄ 2 50.2 10 0.75 AgNO₃ + 1.25 AgCl₄ + 1 HAuCl₄ 24 141.9 11 0.75 AgNO₃ + 1.25 AgCl₄ + 1 HAuCl₄ 100 208.7 ^(a)Moles of CEESO/moles of catalyst (catalyst is based on moles of HAuCl₄ used)

Example 10 Aerobic Oxidation of CEES by POM/HAuCl₄ and Metal Compound/HAuCl₄ Systems

One equivalent of the POM or metal compound was combined with five equivalents of HAuCl₄ in acetonitrile, wherein the total volume was 1 mL. To this solution, 100 equivalents of CEES was added. The reaction was conducted under one atm of O₂ at 298 K. The number of turnovers were calculated at 4 and 11 hours, and the results are summarized in Table 8a.

TABLE 8a Turn- Turn- Entry POM or Metal Compound overs^(a) overs^(b) 1 Na₉PV₆Mo₆O₄₀ 5.6 20.7 2 Na₅CuPW₁₁O₃₉ 59.2 83.6 3 Na₅MnPW₁₁O₃₉ 6.5 29.0 4 K₅CoPW₁₁O₃₉ 38.9 71.9 5 (n-Dec₄)₆HMnNb₃P₂W₁₅O₆₂ 5.1 27.9 6 K₅PMnW₁₁O₃₉ 51.8 76.5 7 Na₅PV₂Mo₁₀O₄₀ 5.0 10.6 8 Na₆PV₃Mo₉O₄₀ 7.0 18.3 9 Na₅H₂PV₄Mo₈O₄₀ 4.4 14.2 10 K₁₂Cu₃(W₉PO₃₄)₂ 5.1 12.2 11 Na₄PVW₁₁O₃₉ 1.6 8.7 12 Na₅FeSiW₁₁O₄₀ 0.9 4.6 13 Na₅SiVW₁₁O₄₀ 0.0 2 3 14 K₁₀Ni₄P₂W₁₂O₆₁ 3.5 7.5 15 K₈Co(II)P₂W₁₂O₆₁ 1.0 2.5 16 K₁₂Pd₃(PW₉O₃₄)₂ 4.2 6.4 17 K₈Cu(II)P₂W₁₂O₆₁ 2.0 4.7 18 Na₄PVMo₁₁O₄₀ 0.0 1 2 19 Na₃PMo₁₂O₄₀ 0.0 0.1 20 H₅PV₂W₁₀O₄₀ 0.0 1.4 21 H₆PV₃W₉O₄₀ 0.0 1.2 22 H₃PV4W₈O₄₀ 0.0 0.9 23 HAuCl₄ 0.0 0.0 24 Na₁₆P₄W₃₀Cu₄O₁₁₂ 1.5 1.5 25 H₂Na₁₄[Fe(III)₂(NaH₂O)₂(P₂W₁₅O₅₆)₂] 1.0 1.6 26 K₁₀Ce(PW₁₁O₃₉)₂ 0.6 0.7 27 K₇CuSiW₁₁O₃₉ 1.0 1.1 28 K₈CoVW₁₁O₄₀ 1.3 1.1 29 K₈Co₂W₁₁O₃₉ 1.5 1.0 30 Na₇CuSiW₁₁O₃₉ 1.1 1.1 31 Na₇NiPW₁₁O₃₉ 0.6 0.9 32 Na₆SiVNbW₁₁O₃₉ 0.7 0.6 33 K₆SiTiW₁₁O₄₀ 0.6 0.4 34 K(NH₄)₆RuBW₁₁O₃₉ 0.7 0.9 35 Na₃AsW₁₂O₄₀ 0.7 0.2 36 K₆FeSiW₁₁O₃₉ 0.9 0.7 37 K₈NiP₂W₁₇O₆₁ 0.9 0.9 38 (Me₄N)₁₀(Co₃SiW₉O₄₀H₆) 1.8 1.9 39 K₁₀Co₄P₂W₁₈O₆₈ 1.3 1.6 40 Na₃V₁₀O₃₈ 1.8 1.7 41 K₁₀Mn₄(PW₉O₃₄)₂ 1.3 1.4 42 K₈P₂W₁₇(NbO₂) 1.1 0.9 43 (NH₄)₆P₂FeW₁₇O₆₁ 0.6 0.5 44 K₇Mn(II)P₂W₁₇O₆₁ 1.0 0.8 45 K₁₀P₂W₁₈Cu₄O₆₈ 1.2 1.9 46 K₅Si(NbO₂)W₁₁O₄₀ 0.9 0.7 47 K₁₂P₂W₁₈Ni₃O₆₈ 1.0 1.8 48 Na₃H₃Mo₉O₃₄ 0.8 0.9 49 Na₆P₄W₃₀Mn(II)₄O₁₁₂ 1.1 1.4 50 (NH₄)₆P₂W₁₈O₆₂ 0.0 0.3 51 (NH₄)₁₇Na(NaSb₉W₂₁)O₈₆ 0.5 1.8 52 CuCl₂ 0.0 0.4 53 FeCl₃ 0.3 0.5 ^(a)Turnovers after 4 hours ^(b)Turnovers after 11 hours

Additional POM and/or metal compounds that were tested can be found in Table 8b.

TABLE 8b Entry Compound A Compound B 1 5 HAuCl₄ 2 Na₄PVMo₁₁O₄₀ 3 Na₄PVMo₁₁O₄₀ 5 HAuCl₄ 4 Na₅PV₂Mo₁₀O₄₀ 5 Na₅PV₂Mo₁₀O₄₀ 5 HAuCl₄ 6 Na₆PV₃Mo₉O₄₀ 7 Na₆PV₃Mo₉O₄₀ 5 HAuCl₄ 8 Na₅H₂PV₄Mo₈O₄₀ 9 Na₅H₃PV₄Mo₈O₄₀ 5 HAuCl₄ 10 Na₉PV₆Mo₆O₄₀ 11 Na₉PV₆Mo₆O₄₀ 5 HAuCl₄ 12 Na₄PVW₁₁O₄₀ 13 Na₄PVW₁₁O₄₀ 5 HAuCl₄ 14 Na₃PMo₁₂O₄₀ 15 Na₃PMo₁₂O₄₀ 5 HAuCl₄ 16 Na₅CuPW₁₁O₃₉ 5 HAuCl₄ 17 (TBA)₅CuPW₁₁O₃₉ 5 HAuCl₄ 18 Na₅MnPW₁₁O₃₉ 19 Na₅MnPW₁₁O₃₉ 5 HAuCl₄ 20 Na₅FeSiW₁₁O₃₉ 21 Na₅FeSiW₁₁O₃₉ 22 Na₅SiVW₁₁O₄₀ 23 Na₅SiVW₁₁O₄₀ 5 HAuCl₄ 24 Na₅PV₂W₁₀O₄₀ 25 Na₅PV₂W₁₀O₄₀ 5 HAuCl₄ 26 Na₆PV₃W₉O₄₀ 27 Na₆PV₃W₉O₄₀ 5 HAuCl₄ 28 Na₇PV₄W₈O₄₀ 29 Na₇PV₄W₈O₄₀ 5 HAuCl₄ 30 Na₁₆P₄W₃₀Cu₄O₁₁₂ 31 Na₁₆P₄W₃₀Cu₄O₁₁₂ 5 HAuCl₄ 32 H₂Na₁₄[Fe(III)₂(NaH₂O)₂(P₂W₁₅O₅₆)₂ 33 H₂Na₁₄[Fe(III)₂(NaH₂O)₂(P₂W₁₅O₅6)₂ 5 HAuCl₄ 34 K₁₀Ce(PW₁₁O₃₉)₂ 35 K₁₀Ce(PW₁₁O₃₉)₂ 5 HAuCl₄ 36 K₇CuSiW₁₁O₃₉ 37 K₇CuSiW₁₁O₃₉ 5 HAuCl₄ 38 K₈CoVW₁₁O₃₉ 39 K₈CoVW₁₁O₃₉ 5 HAuCl₄ 40 K₅CoPW₁₁O₃₉ 41 K₅CoPW₁₁O₃₉ 5 HAuCl₄ 42 K₈Co₂W₁₁O₃₉ 43 K₈Co₂W₁₁O₃₉ 5 HAuCl₄ 44 (NDec₄)₆HMnNb₃P₂W₁₅O₆₂ 45 (NDec₄)₆HMnNb₃P₂W₁₅O₆₂ 5 HAuCl₄ 46 Na₇CuSiW₁₁O₃₉ 47 Na₇CuSiW₁₁O₃₉ 5 HAuCl₄ 48 Na₅NiPW₁₁O₃₉ 49 Na₅NiPW₁₁O₃₉ 5 HAuCl₄ 50 Na₆SiVNbW₁₁O₃₉ 51 Na₆SiVNbW11O₃₉ 5 HAuCl₄ 52 K₅PMnW₁₁O₃₉ 53 K₅PMnW₁₁O₃₉ 5 HAuCl₄ 54 K₆SiTiW₁₁O₄₀ 55 K₆SiTiW₁₁O₄₀ 5 HAuCl₄ 56 K(NH₄)₆RuBW₁₁O₃₉ 57 K(NH₄)₆RuBW₁₁O₃₉ 5 HAuCl₄ 58 Na₃AsW₁₂O₄₀ 59 Na₃AsW₁₂O₄₀ 5 HAuCl₄ 60 K₆FeSiW₁₁O₃₉ 61 K₆FeSiW₁₁O₃₉ 5 HAuCl₄ 62 K₈NiP₂W₁₇O₆₁ 63 K₈NiP₂W₁₇O₆₁ 5 HAuCl₄ 64 (ME₄N)₁₀(Co₃SiW₉O₄₀H₆) 65 (ME₄N)₁₀(Co₃SiW₉O₄₀H₆) 5 HAuCl₄ 66 K₁₀Co₄P₂W₁₈O₆₈ 67 K₁₀Co₄P₂W₁₈O₆₈ 5 HAuCl₄ 68 Na₃V₁₀O₂₈ 69 Na₃V₁₀O₂₈ 5 HAuCl₄ 70 K₁₀(Mn₄)(PW₉O₃₄)₂ 71 K₁₀(Mn₄)(PW₉O₃₄)₂ 5 HAuCl₄ 72 K₁₂Cu₃(W₉PO₃₄)₂ 73 K₁₂Cu₃(W₉PO₃₄)₂ 5 HAuCl₄ 74 K₁₀Ni₄P₂W₁₇O₆₁ 75 K₁₀Ni₄P₂W₁₇O₆₁ 5 HAuCl₄ 76 K₈P₂W₁₇(NbO₂) 77 K₈P₂W₁₇(NbO₂) 5 HAuCl₄ 78 (NH₄)₆P₂FeW₁₇O₆₁ 79 (NH₄)₆P₂FeW₁₇O₆₁ 5 HAuCl₄ 80 K₈Co(II)P₂W₁₇O₆₁ 81 K₈Co(II)P₂W₁₇O₆₁ 5 HAuCl₄ 82 K₁₂Pd₃(PW₉O₃₄)₂ 83 K₁₂Pd₃(PW₉O₃₄)₂ 5 HAuCl₄ 84 K₇Mn(II)P₂W₁₇O₆₁ 5 HAuCl₄ 85 K₁₀P₂W₁₈Cu₄O₆₈ 5 HAuCl₄ 86 K₈Cu(II)P₂W₁₇O₆₁ 5 HAuCl₄ 87 K₅Si(NbO₂)W₁₁O₄₀ 5 HAuCl₄ 88 K₁₂P₂W₁₈Ni₃O₆₈ 5 HAuCl₄ 89 Na₃H₆Mo₉O₃₄ 5 HAuCl₄ 90 Na₆P₄W₃₀Mn(II)₄O₁₁₂ 5 HAuCl₄ 91 (NH₄)₆P₂W₁₈O₆₂ + 5HAuCl₄ 5 HAuCl₄ 92 (NH₄)₁₇Na(NaSb₉W₂₁)O₈₆ 5 HAuCl₄ 93 5 Cu(acetate)₂ 94 Na₅PV₂Mo₁₀O₄₀ 5 Cu(acetate)₂ 95 5 Co(II)Acac 96 Na₅PV₂Mo₁₀O₄₀ 5 Co(II)Acac 97 5 Fe(III)Acac 98 Na₅PV₂Mo₁₀O₄₀ 5 Fe(III)Acac 99 5 MnO₂ 100 Na₅PV₂Mo₁₀O₄₀ 5 MnO₂ 101 5 CuCl₂ 102 Na₅PV₂Mo₁₀O₄₀ 5 CuCl₂ 103 5 FeCl₃ 104 Na₅PV₂Mo₁₀O₄₀ 5 FeCl₃ 105 5 CrCl₃ 106 Na₅PV₂Mo₁₀O₄₀ 5 CrCl₃ 107 5 CeCl₃ 108 Na₅PV₂Mo₁₀O₄₀ 5 CeCl₃ 109 Na₉PV₆Mo₆O₄₀ 5 FeCl₃ 110 Na₉PV₆Mo₆O₄₀ 5 CuCl₃ 111 Na₉PV₆Mo₆O₄₀ 112 K₁₂Pd₃(PW₉O₃₆)₂ 5 FeCl₃ 113 K₁₂Pd₃(PW₉O₃₆)₂ 5 CuCl₂ 114 K₁₂Pd₃(PW₉O₃₆)₂ 115 Na₅CuPW₁₁O₃₉ 116 Na₅CuPW₁₁O₃₉ 5 Cr(NO₃)₃ 117 5 CrNO₃ 118 Na₅CuPW₁₁O₃₉ 5 Co(NO₃)₂ 119 5 Co(NO₃)₂ 120 5 Zn(NO₃)₂ 121 Na₅CuPW₁₁O₃₉ 5 Zn(NO₃)₂ 122 Na₅CuPW₁₁O₃₉ 5 Cu(NO₃)₂ 123 5 Cu(NO₃)₂ 124 Na₅CuPW₁₁O₃₉ 5 Zn(NO3)3 125 Na₅CuW₁₁O₃₉ 5 Cu(acetate)₂ 126 Na₅CuW₁₁O₃₉ 5 Fe(acetate)₂ 127 Na₅CuW11O₃₉ 5 MnO₂ 128 5 NaNO₃ 129 Li₅PVW₁₁O₄₀ 5 HAuCl₄ 130 AgNO₃ 131 AgNO₃ 5 HAuCl₄ 132 NaNO₃ 5 HAuCl₄ 133 NaClO₄ 5 HAuCl₄ 134 AgClO₄ 5 HAuCl₄ 135 LiClO₄ 5 HAuCl₄ 136 5 (NH₄)₂Ce(NO₃)₆ 137 Na₅PVMo₁₁O₄₀ 5 (NH₄)₂Ce(NO₃)₆ 138 Na₅CuPW₁₁O₃₉ 5 (NH₄)₂Ce(NO₃)₆ 139 Na₅PVMo₁₁O₄₀ 5 CoSO₄ 140 Na₅CuPW₁₁O₃₉ 5 CoSO₄ 141 Na₅PVMo₁₁O₄₀ 5 Ce(SO₄)₂ 142 Na₅CuPW₁₁O₃₉ 5 Ce(SO₄)₂ 143 Na₅PVMo₁₁O₄₀ 5 H₂PtCl₆ 144 Na₅CuPW11O₃₉ 5 H₂PtCl₆ 145 Na₅PVMo₁₁O₄₀ 5 Pd(NO₃)₂ 146 Na₅CuPW₁₁O₃₉ 5 Pd(NO₃)₂ 147 Na₅PVMo₁₁O₄₀ 5 RhCl₃ 148 Na₅CuPW₁₁O₃₉ 5 RhCl₃ 149 Na₅PVMo₁₁O₄₀ 5 ReO₂ 150 Na₅CuPW₁₁O₃₉ 5 ReO₂

Example 11 Oxidation of CEES to CEESO by Metal Compounds (non-POM)

(a) Determining the Stoichiometry of O₂ in the Catalytic Oxidation of CEES. A Schlenk flask fitted with septum was attached to a manometer and purged with O₂. To the flask containing 1.36 mL of acetonitrile, solutions (all in acetonitrile) of 0 200 mL of (NEt₄)AuCl₂ (5.0×10⁻⁶ mol), 0.188 mL of AgClO₄ solution (1.0×10⁵ mol), 0.094 mL NBu₄NO₃ solution (5.0×10⁻⁶ mol), 0.166 mL 1,3-dichlorobenzene (7 5 ×10⁻⁴ mol) (internal standard for GC), and 0.084 mL CEES (3 8×10⁻⁴ mol) were added The consumption of O₂ was recorded, and aliquots were periodically taken and injected into the GC. The stoichiometry of O₂ consumption was established using a manometer to determine the amount of O₂ consumed while simultaneously monitoring CEESO formation with a gas chromatograph. FIG. 1 reveals that one equivalent of the CEESO formed corresponds to 0.5 equivalents of O₂.

(b) Cream Formulation Reactions. Experiments were performed using the perfluorinated oil, Galden DO2, and Fomblin perfluorinated polyether oil as “solvent,” both of which are components of the cream. Samples were prepared by adding components together, dissolving in a minimal amount of acetonitrile, stirring for 10 minutes, and then removing the solvent by vacuum.

In all the cases where (NEt₄)AuCl₂ was used as the gold compound, 1.25×10⁻⁵ mol of the gold compound was used. The other components which were varied in quantities were NBu₄NO₃ (1.25×10⁻⁵–1.25×10 mol), and a CUSO₄ (1.25×10⁵–1.25×10⁻⁴ mol) (Table 9). The gold, copper, and/or nitrate salts were admixed in acetonitrile, then the solvent was removed by vacuum. After the mixture was dried by vacuum in a Schlenk flask, the flask is attached to the manometer and the apparatus is purged with O₂. After purging, 7.0 mL of the perfluorinated fluid was added to the flask. The system was equilibrated to atmospheric pressure then sealed from any external atmosphere. Through the septum 0.05 mL (4.2×10⁻⁴ mol) of CEES was added and the system was monitored for O₂ consumption. Table 9 shows CEESO formation after 1 hour using various cream formulations (7 0 mL Galden DO2).

TABLE 9^(a) [Au] [NO₃] [Cu⁺²] [CEESO formed] 0 1.25 1.25 3.62 1.25 1.25 1.25 5.80 0 2.50 2.50 5.00 1.25 2.50 2.50 8.06 0 5.00 7.25 8.06 1.25 5.00 7.25 16.20 0 10.00 12.50 10.60 1.25 10.00 12.50 18.70 ^(a)All concentrations expressed in 10⁻⁵ mol.

Another experiment was performed using Fomblin as the “solvent.” In this case, 1.0 mL of Fomblin, 0.005 g of (NEt₄)AuCl₂ (1.25×10⁻⁵ mol), was admixed in with varying amounts of CuSO₄, MnSO₄, VOSO₄, Ti(SO₄)₂, Fe₂(SO₄)₃, NiSO₄, ZnSO₄, Cr₂(SO₄)₃, MgSO₄, CoSO₄, Pd(NO₃)₄, Na₂SO₃, and/or NBu₄NO₃. The catalyst was prepared and the experiment was performed using the same method as earlier reported Table 10 reveals CEESO formation in PFPE Surfactant (1.0 mL Fomblin) using various metal compounds. The metal compounds are abbreviated for simplicity sake. For example, metal compound 1 Au/1 Cu(II)/1 NO₃ was prepared by mixing one equivalent each of (NEt₄)AuCl₂, CuSO₄, and NBu₄NO₃.

TABLE 10 Turnovers of CEESO after 10 min Metal Compound (based on Au) 1Au/1Cu(II)/1NO₃ 17 1Au/2Cu(II)/1NO₃ 28 1Au/1Cu(II)/2NO₃ 115 1Au/2Cu(II)/2NO₃ 155 1Au/1Cu(II)/3NO₃ 155 1Au/1Fe(III)/3NO₃ 142 1Au/2Mn(II)/3NO₃ 164 1Au/2Ti(IV)/3NO₃ 142 1Au/2Co(II)/3NO₃ 177 1Au/4NO₃ 185 1Au/2Cu(II)/3NO₃ 181 1Au/2Cu(II)/4NO₃ 195 1Au/3Cu(II)/3NO₃ 165 2Cu(II)/3NO₃ 28 1Au/3NO₃ 150 1Fe(III)/3NO₃ 19 1Au/2V(IV)/3NO₃ 160 1Au/2Ni(II)/3NO₃ 140 1Au/2Ag(II)/3NO₃ 184

FIG. 2 shows CEESO formation as a function of time for 1 Au/2 Cu(II)/3 NO₃, 2 Cu(II)/3 NO₃, and 1 Au/3 NO₃. From the data in Table 10 and FIG. 2, it is clear that there was a synergistic effect when certain redox active metals were added to the Au/NO₃ system. For example, one of the most active systems, 1 Au/2 Cu(II)/3 NO₃ was 3 8 and 6.5 times more effective after 10 minutes of reaction time than when only 2 of the components were used, 1 Au/3 NO₃ and 2 Cu(II)/3 NO₃ respectively. Also, FIG. 2 shows that inhibition was less pronounced in the three component system. Another important aspect of this system is that the oxidation terminates to the sulfoxide without continued oxidation to yield the sulfone. This is important as it relates to toxicity issues as it is believed that the sulfoxide of mustard gas is significantly less toxic than the corresponding sulfone.

Example 12 Synthesis, Characterization, and Reactivity of Organo-Modified POMs

(a) Synthesis of Ag₂[V₆O₁₃((OCH₂)₃CCH₃)₂](Ag Me cap)

Na₂[V₆O₁₃((OCH₂)₃CCH₃)₂](Na Me cap, 0.480 g) was dissolved in ˜4 mL or distilled water. This was filtered over a medium fritted funnel to remove any undissolved POM. To the dark red-orange solution was added AgNO₃ (0 215 g) with stirring. An orange-red precipitate formed immediately. The crude product was separated by suction filtration over a medium frit, washed with room temperature water and ether. The product was dried over night in vacuo. Crystals were grown by diffusing ether into an acetonitrile solution of the crude product at room temperature. ⁵¹V NMR (0.04 g dissolved in 2.0 mL of MeCN) −499.232 ppm (singlet). Solid-state IR (KBr pellet, 1400–400 cm⁻¹) 1452.11 (m), 1390.47 (w), 1200.43 (w), 1128.53 (m), 1015.5 (s), 953.9 (vs), 820.36 (sh), 794.68 (s), 712.5 (s), 614.91 (sh), 584.09 (m), 424.87 (s).

(b) Synthesis of Co[V₆O₁₃((OCH₂)₃CCH₃)₂](Co Me cap)

The same procedure for the synthesis of Ag₂[V₆O₁₃((OCH₂)₃CCH₃)₂] was followed, except CoCl₂ was added to form the Co salt of the POM. Crystals were grown from diffusing isopropyl alcohol into a MeCN solution of crude product. ⁵¹V NMR (0.04 g dissolved in 2.0 mL of MeCN) −500.3 ppm (singlet). Solid-state IR (KBr pellet, 1400–400 cm⁻¹) 1452.11 (m), 1390.47 (w), 1200.43 (w), 1128.53 (m), 1015 5 (s), 953.9 (vs), 820.36 (sh), 794.68 (s), 712.5 (s), 614.91 (sh), 584.09 (m), 424.87 (s).

(c) Reactivity of Organo-Modified POMs

Table 11 lists the oxidation of tetrahydrothiopbene (THT) by t-butylhydroperoxide (TBHP) catalyzed by the transition metal salts of Me-capped V₆O₁₃ The oxidations were performed by dissolving the particular salt in acetonitrile to give lightly colored orange-yellow solutions. The solutions were placed in 24-mL vials fitted with PTFE septa. THT and TBHP were then syringed in and the reactions were monitored by quantitative GC. Reactions were stirred at room temperature

TABLE 11 Room Temperature Oxidation of THT to THTO by TBHP Catalyzed by Transition Metal Salts of Me Capped V₆O₁₃ after 48 Hours. Mols of Mols of Turnover Catalyst catalyst, × 10⁻⁶ THTO, × 10⁻⁵ number^(b) Na Me cap 1.76 6.03 34.3 Ag Me cap 1.87 5.59 30.0 Co Me cap 1.61 6.33 39.3 AgNO₃ 14.1 1.06 0.754 CoCl₂ 39.5 2.25 0.570 blank^(a) NA 0 0 ^(a)blank reaction: 3.0 mL of MeCN, 0.018 mL of THT, 0.010 mL of internal reference ^(b)Turnover number = (mols of THTO)/(mols of catalyst) × 100

Throughout this application, various publications are referenced. The disclosures of these publications in their entireties are hereby incorporated by reference into this application in order to more fully describe the state of the art to which this invention pertains.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope or spirit of the invention. Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. It is intended that the specification and examples be considered as exemplary only. 

1. A modified polyoxometalate, wherein the modified polyoxometalate comprises the admixture of: (1) a pre-modified polyoxometalate selected from the group consisting of H₅PV₂Mo₁₀O₄₀, Na₅PV₂Mo₁₀O₄₀, Li₅PV₂Mo₁₀O₄₀, K₅PV₂Mo₁₀O₄₀, and combinations thereof; and (2) one member selected from the group consisting of (i) (NH₄)₂Ce(NO₃)₆, (ii) combination of (NH₄)₂Ce(NO₃)₆ and HAuCl₄, (iii) combination of (NH₄)₂Ce(NO₃)₆ and H₂PtCl₆, and (iv) AgNO₃; wherein (1) and (2) do not react with one another.
 2. The modified polyoxometalate of claim 1, wherein (2) is (NH₄)₂Ce(NO₃)₆.
 3. The modified polyoxometalate of claim 1, wherein (2) is the combination of (NH₄)₂Ce(NO₃)₆ and HAuCl₄.
 4. The modified polyoxometalate of claim 1, wherein (2) is the combination of (NH₄)₂Ce(NO₃)₆ and H_(PtCl) ₆.
 5. The modified polyoxometalate of claim 1, wherein (2) is AgNO₃.
 6. A modified polyoxometalate, wherein the modified polyoxometalate comprises the admixture of: (1) a pre-modified polyoxometalate selected from the group consisting of Na₄PVMo₁₁O₄₀, Na₅PV₂Mo₁₀O₄₀, Na₆PV₃Mo₉O₄₀, Na₅H₂PV₄W₈O₄₀, Na₉PV₆Mo₆O₄₀, Na₅CuPW₁₁O₃₉, Na₅MnPW₁₁O₄₀, K₅CoPW₁₁O₃₉, (n-Dec₄)₆HMnNb₃P₂W₁₅O₆₂ and K₁₂Cu₃(W₉PO₃₄)₂, and (2) HAuCl₄; wherein (1) and (2) do not react with one another. 